CA2299104C - Improved recovery and transportation of heavy crude oils - Google Patents
Improved recovery and transportation of heavy crude oils Download PDFInfo
- Publication number
- CA2299104C CA2299104C CA002299104A CA2299104A CA2299104C CA 2299104 C CA2299104 C CA 2299104C CA 002299104 A CA002299104 A CA 002299104A CA 2299104 A CA2299104 A CA 2299104A CA 2299104 C CA2299104 C CA 2299104C
- Authority
- CA
- Canada
- Prior art keywords
- amine
- mixture
- viscosity
- heavy crude
- amines
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000010779 crude oil Substances 0.000 title claims abstract description 20
- 238000011084 recovery Methods 0.000 title abstract description 15
- 150000001412 amines Chemical class 0.000 claims abstract description 39
- 238000010438 heat treatment Methods 0.000 claims abstract description 16
- 239000002738 chelating agent Substances 0.000 claims abstract description 13
- -1 alkyl primary amines Chemical group 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 24
- 229920000768 polyamine Polymers 0.000 claims description 24
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 9
- 125000001931 aliphatic group Chemical group 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- 125000003342 alkenyl group Chemical group 0.000 claims description 8
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical class OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- 150000007513 acids Chemical class 0.000 claims description 3
- 125000003277 amino group Chemical group 0.000 claims description 3
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 claims description 3
- 229920006395 saturated elastomer Polymers 0.000 claims description 3
- 150000003335 secondary amines Chemical class 0.000 claims description 3
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims description 2
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical class NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 claims description 2
- LTHNHFOGQMKPOV-UHFFFAOYSA-N 2-ethylhexan-1-amine Chemical compound CCCCC(CC)CN LTHNHFOGQMKPOV-UHFFFAOYSA-N 0.000 claims description 2
- XBPCUCUWBYBCDP-UHFFFAOYSA-N Dicyclohexylamine Chemical compound C1CCCCC1NC1CCCCC1 XBPCUCUWBYBCDP-UHFFFAOYSA-N 0.000 claims description 2
- 229920000388 Polyphosphate Polymers 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 150000003973 alkyl amines Chemical class 0.000 claims description 2
- XTAZYLNFDRKIHJ-UHFFFAOYSA-N n,n-dioctyloctan-1-amine Chemical compound CCCCCCCCN(CCCCCCCC)CCCCCCCC XTAZYLNFDRKIHJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 150000002923 oximes Chemical class 0.000 claims description 2
- 150000002989 phenols Chemical class 0.000 claims description 2
- 235000011007 phosphoric acid Nutrition 0.000 claims description 2
- 150000003016 phosphoric acids Chemical class 0.000 claims description 2
- 239000001205 polyphosphate Substances 0.000 claims description 2
- 235000011176 polyphosphates Nutrition 0.000 claims description 2
- 230000002441 reversible effect Effects 0.000 claims description 2
- 150000003464 sulfur compounds Chemical class 0.000 claims description 2
- ABVVEAHYODGCLZ-UHFFFAOYSA-N tridecan-1-amine Chemical group CCCCCCCCCCCCCN ABVVEAHYODGCLZ-UHFFFAOYSA-N 0.000 claims description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical class NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 claims 1
- 150000001735 carboxylic acids Chemical class 0.000 claims 1
- 229960001484 edetic acid Drugs 0.000 claims 1
- 150000002678 macrocyclic compounds Chemical class 0.000 claims 1
- 239000013522 chelant Substances 0.000 abstract description 6
- 239000000203 mixture Substances 0.000 description 61
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 24
- 230000015572 biosynthetic process Effects 0.000 description 13
- 238000005755 formation reaction Methods 0.000 description 13
- 239000003921 oil Substances 0.000 description 13
- 150000001875 compounds Chemical class 0.000 description 11
- 239000000654 additive Substances 0.000 description 10
- 230000000996 additive effect Effects 0.000 description 10
- 238000010992 reflux Methods 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 9
- 239000011541 reaction mixture Substances 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 8
- 230000009467 reduction Effects 0.000 description 8
- 239000000523 sample Substances 0.000 description 8
- WTFAGPBUAGFMQX-UHFFFAOYSA-N 1-[2-[2-(2-aminopropoxy)propoxy]propoxy]propan-2-amine Chemical compound CC(N)COCC(C)OCC(C)OCC(C)N WTFAGPBUAGFMQX-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000003208 petroleum Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000010793 Steam injection (oil industry) Methods 0.000 description 5
- 125000002947 alkylene group Chemical group 0.000 description 5
- 238000002347 injection Methods 0.000 description 5
- 239000007924 injection Substances 0.000 description 5
- QIJIUJYANDSEKG-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-amine Chemical compound CC(C)(C)CC(C)(C)N QIJIUJYANDSEKG-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 239000003085 diluting agent Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000003350 kerosene Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 239000011269 tar Substances 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 229920001429 chelating resin Polymers 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 150000004985 diamines Chemical class 0.000 description 3
- 238000007865 diluting Methods 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- ICSNLGPSRYBMBD-UHFFFAOYSA-N 2-aminopyridine Chemical compound NC1=CC=CC=N1 ICSNLGPSRYBMBD-UHFFFAOYSA-N 0.000 description 2
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical compound CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 2
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 2
- AAIUWVOMXTVLRG-UHFFFAOYSA-N 8,8-dimethylnonan-1-amine Chemical compound CC(C)(C)CCCCCCCN AAIUWVOMXTVLRG-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 238000010795 Steam Flooding Methods 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- LHIJANUOQQMGNT-UHFFFAOYSA-N aminoethylethanolamine Chemical compound NCCNCCO LHIJANUOQQMGNT-UHFFFAOYSA-N 0.000 description 2
- 239000003849 aromatic solvent Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- XXUJMEYKYHETBZ-UHFFFAOYSA-N ethyl 4-nitrophenyl ethylphosphonate Chemical compound CCOP(=O)(CC)OC1=CC=C([N+]([O-])=O)C=C1 XXUJMEYKYHETBZ-UHFFFAOYSA-N 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- LSHROXHEILXKHM-UHFFFAOYSA-N n'-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCN LSHROXHEILXKHM-UHFFFAOYSA-N 0.000 description 2
- CRSOQBOWXPBRES-UHFFFAOYSA-N neopentane Chemical compound CC(C)(C)C CRSOQBOWXPBRES-UHFFFAOYSA-N 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 239000003209 petroleum derivative Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 150000003141 primary amines Chemical class 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 2
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 description 2
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 description 2
- 241000894007 species Species 0.000 description 2
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 2
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- BAERPNBPLZWCES-UHFFFAOYSA-N (2-hydroxy-1-phosphonoethyl)phosphonic acid Chemical compound OCC(P(O)(O)=O)P(O)(O)=O BAERPNBPLZWCES-UHFFFAOYSA-N 0.000 description 1
- GOLAKLHPPDDLST-HZJYTTRNSA-N (9z,12z)-octadeca-9,12-dien-1-amine Chemical compound CCCCC\C=C/C\C=C/CCCCCCCCN GOLAKLHPPDDLST-HZJYTTRNSA-N 0.000 description 1
- UATFHWVUSDADRL-FPLPWBNLSA-N (z)-hexadec-9-en-1-amine Chemical compound CCCCCC\C=C/CCCCCCCCN UATFHWVUSDADRL-FPLPWBNLSA-N 0.000 description 1
- JTQQDDNCCLCMER-CLFAGFIQSA-N (z)-n-[(z)-octadec-9-enyl]octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCNCCCCCCCC\C=C/CCCCCCCC JTQQDDNCCLCMER-CLFAGFIQSA-N 0.000 description 1
- SHXHPUAKLCCLDV-UHFFFAOYSA-N 1,1,1-trifluoropentane-2,4-dione Chemical compound CC(=O)CC(=O)C(F)(F)F SHXHPUAKLCCLDV-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- PWGJDPKCLMLPJW-UHFFFAOYSA-N 1,8-diaminooctane Chemical compound NCCCCCCCCN PWGJDPKCLMLPJW-UHFFFAOYSA-N 0.000 description 1
- FJLUATLTXUNBOT-UHFFFAOYSA-N 1-Hexadecylamine Chemical compound CCCCCCCCCCCCCCCCN FJLUATLTXUNBOT-UHFFFAOYSA-N 0.000 description 1
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 description 1
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- 125000006039 1-hexenyl group Chemical group 0.000 description 1
- 125000006023 1-pentenyl group Chemical group 0.000 description 1
- ZCBIFHNDZBSCEP-UHFFFAOYSA-N 1H-indol-5-amine Chemical compound NC1=CC=C2NC=CC2=C1 ZCBIFHNDZBSCEP-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- BCKYDNXQBUZUDJ-UHFFFAOYSA-N 2,4,4-trimethyl-n-(2,4,4-trimethylpentan-2-yl)pentan-2-amine Chemical compound CC(C)(C)CC(C)(C)NC(C)(C)CC(C)(C)C BCKYDNXQBUZUDJ-UHFFFAOYSA-N 0.000 description 1
- TYFSYONDMQEGJK-UHFFFAOYSA-N 2-(2,2-dihydroxyethylamino)acetic acid Chemical compound OC(O)CNCC(O)=O TYFSYONDMQEGJK-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- GHKSKVKCKMGRDU-UHFFFAOYSA-N 2-(3-aminopropylamino)ethanol Chemical compound NCCCNCCO GHKSKVKCKMGRDU-UHFFFAOYSA-N 0.000 description 1
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- URDCARMUOSMFFI-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(2-hydroxyethyl)amino]acetic acid Chemical compound OCCN(CC(O)=O)CCN(CC(O)=O)CC(O)=O URDCARMUOSMFFI-UHFFFAOYSA-N 0.000 description 1
- PAOXFRSJRCGJLV-UHFFFAOYSA-N 2-[4-(2-aminoethyl)piperazin-1-yl]ethanamine Chemical compound NCCN1CCN(CCN)CC1 PAOXFRSJRCGJLV-UHFFFAOYSA-N 0.000 description 1
- WCSLPBBQHFXWBW-UHFFFAOYSA-N 2-[[2-[(2-hydroxyphenyl)methylideneamino]cyclohexyl]iminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NC1C(N=CC=2C(=CC=CC=2)O)CCCC1 WCSLPBBQHFXWBW-UHFFFAOYSA-N 0.000 description 1
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- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 1
- LAIUFBWHERIJIH-UHFFFAOYSA-N 3-Methylheptane Chemical class CCCCC(C)CC LAIUFBWHERIJIH-UHFFFAOYSA-N 0.000 description 1
- 125000006027 3-methyl-1-butenyl group Chemical group 0.000 description 1
- SPVVMXMTSODFPU-UHFFFAOYSA-N 3-methyl-n-(3-methylbutyl)butan-1-amine Chemical compound CC(C)CCNCCC(C)C SPVVMXMTSODFPU-UHFFFAOYSA-N 0.000 description 1
- WZUUZPAYWFIBDF-UHFFFAOYSA-N 5-amino-1,2-dihydro-1,2,4-triazole-3-thione Chemical compound NC1=NNC(S)=N1 WZUUZPAYWFIBDF-UHFFFAOYSA-N 0.000 description 1
- 239000005725 8-Hydroxyquinoline Substances 0.000 description 1
- SAIKULLUBZKPDA-UHFFFAOYSA-N Bis(2-ethylhexyl) amine Chemical compound CCCCC(CC)CNCC(CC)CCCC SAIKULLUBZKPDA-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000009261 D 400 Substances 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
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- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical class ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- RVRHBLSINNOLPI-UHFFFAOYSA-N Lythridin Natural products COc1ccc(cc1OC)C2CC(CC3CCCCN23)OC(=O)CC(O)c4ccc(O)cc4 RVRHBLSINNOLPI-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 1
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 description 1
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 208000037062 Polyps Diseases 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000003282 alkyl amino group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- IMUDHTPIFIBORV-UHFFFAOYSA-N aminoethylpiperazine Chemical compound NCCN1CCNCC1 IMUDHTPIFIBORV-UHFFFAOYSA-N 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 125000001204 arachidyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000010009 beating Methods 0.000 description 1
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- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- HLVXFWDLRHCZEI-UHFFFAOYSA-N chromotropic acid Chemical compound OS(=O)(=O)C1=CC(O)=C2C(O)=CC(S(O)(=O)=O)=CC2=C1 HLVXFWDLRHCZEI-UHFFFAOYSA-N 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- LTNZEXKYNRNOGT-UHFFFAOYSA-N dequalinium chloride Chemical compound [Cl-].[Cl-].C1=CC=C2[N+](CCCCCCCCCC[N+]3=C4C=CC=CC4=C(N)C=C3C)=C(C)C=C(N)C2=C1 LTNZEXKYNRNOGT-UHFFFAOYSA-N 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- IRDLUHRVLVEUHA-UHFFFAOYSA-N diethyl dithiophosphate Chemical compound CCOP(S)(=S)OCC IRDLUHRVLVEUHA-UHFFFAOYSA-N 0.000 description 1
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
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- IMENJLNZKOMSMC-UHFFFAOYSA-N n'-[2-[2-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCNCCNCCN IMENJLNZKOMSMC-UHFFFAOYSA-N 0.000 description 1
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- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- 125000001196 nonadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 235000005985 organic acids Nutrition 0.000 description 1
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- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- PEUGKEHLRUVPAN-UHFFFAOYSA-N piperidin-3-amine Chemical compound NC1CCCNC1 PEUGKEHLRUVPAN-UHFFFAOYSA-N 0.000 description 1
- LTEKQAPRXFBRNN-UHFFFAOYSA-N piperidin-4-ylmethanamine Chemical compound NCC1CCNCC1 LTEKQAPRXFBRNN-UHFFFAOYSA-N 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 150000003139 primary aliphatic amines Chemical class 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- ORIHZIZPTZTNCU-YVMONPNESA-N salicylaldoxime Chemical compound O\N=C/C1=CC=CC=C1O ORIHZIZPTZTNCU-YVMONPNESA-N 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
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- 239000000243 solution Substances 0.000 description 1
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- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- TXBBUSUXYMIVOS-UHFFFAOYSA-N thenoyltrifluoroacetone Chemical compound FC(F)(F)C(=O)CC(=O)C1=CC=CS1 TXBBUSUXYMIVOS-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229960001124 trientine Drugs 0.000 description 1
- QFKMMXYLAPZKIB-UHFFFAOYSA-N undecan-1-amine Chemical compound CCCCCCCCCCCN QFKMMXYLAPZKIB-UHFFFAOYSA-N 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 210000003462 vein Anatomy 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000002569 water oil cream Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003738 xylenes Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/22—Organic compounds containing nitrogen
- C10L1/221—Organic compounds containing nitrogen compounds of uncertain formula; reaction products where mixtures of compounds are obtained
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/24—Organic compounds containing sulfur, selenium and/or tellurium
- C10L1/2493—Organic compounds containing sulfur, selenium and/or tellurium compounds of uncertain formula; reactions of organic compounds (hydrocarbons, acids, esters) with sulfur or sulfur containing compounds
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/26—Organic compounds containing phosphorus
- C10L1/2691—Compounds of uncertain formula; reaction of organic compounds (hydrocarbons acids, esters) with Px Sy, Px Sy Halz or sulfur and phosphorus containing compounds
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
- F17D—PIPE-LINE SYSTEMS; PIPE-LINES
- F17D1/00—Pipe-line systems
- F17D1/08—Pipe-line systems for liquids or viscous products
- F17D1/16—Facilitating the conveyance of liquids or effecting the conveyance of viscous products by modification of their viscosity
- F17D1/17—Facilitating the conveyance of liquids or effecting the conveyance of viscous products by modification of their viscosity by mixing with another liquid, i.e. diluting
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
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- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Water Supply & Treatment (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Public Health (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Lubricants (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Fats And Perfumes (AREA)
Abstract
Novel amine-chelate complexes are useful in significantly reducing the viscosity of heavy crude oils, facilitating the recovery and transportation of such heavy crude oils. The amine-chelate complexes are formed by heating together an organic amine with a chelating agent.
Description
IMPROVED RECOVERY AND TRANSPORTATION OF HEAVY CRUDE OILS
BACKGROUI~TD OF THE INVENTION
The present invention relates generally to the field of petroleum production and transportation. In particular, the present invention relates to the use of certain amine-chelate complexes to reduce significantly the viscosity of heavy crude oils.
Heavy crude oils ("HCO" or "HCOs") constitute a significant portion of the known global petroleum reserves. Vast deposits of HCOs are located in Colombia, Venezuela, Mexico and Canada. HCOs are highly viscous or solid at ambient temperature, and have a gravity of 20 or less on the API (American Petroleum Institute) density scale. HCOs include the high molecular weight hydrocarbons referred to as "tars," "petroleum tars" or "tar sands," such as the deposit known as the Athabasca Tar Sands in Alberta, Canada. In comparison, "conventional" or "light" crudes such as those found in the Middle East typically have API
gravity of 37 or greater.
In addition to being more viscous than conventional crude oils, certain HCOs are rich in asphaltenes, metals and resins. While there is a wide variety in HCO
composition and physical properties, many HCOs typically contain high levels of sulfur, nitrogen, nickel and vanadium, and are rich in the condensed polyaromatic compounds which react readily to form coke. The presence of these types of compounds in HCOs can lead to various problems in the recovery, transportation, treatment and refining of crude oils.
In order for the extraction and transportation of HCOs to be economically viable, the flow resistance of the HCO must be reduced sufficiently to enable the use of reasonably sized wellbores, pipelines and pumping equipment. Some common methods of reducing flow resistance include: heat, dilution, partial field upgrading, water-emulsification, and lubrication and core-annular flow. Heat is generally applied using steam generated at or near the well site.
The primary method for recovering HCOs from oil-bearing formations is steam injection, also know as steam flooding. Although there are numerous variations, there are two basic techniques: the "huff and puff" (or "push-pull") involves injecting steam into a formation, alternating with back-producing the oil through the same well; and the "steam drive" involves injecting steam into a formation through one well (an "injection' well) and producing the oil from a different well (a "production' or "recovery" well). Variations include the number and type of wells, as well as their location and configuration.
The steam injection method is useful in recovery of HCOs because relatively small increases in the temperature of HCOs result in relatively large reductions in viscosity. This also explains some of the limitations and problems of this method.
For example, it is expensive but necessary to locate steam generators near the injection wells. In addition, heating of the oil-bearing formation also results in heating of the adjacent rock. Third, there is a lower limit to the well depth to which the steam injection can be effectively applied, since the steam cools and liquefies as it proceeds down the well-bore. This well depth limit will depend on the particular conditions at the well site, but will generally be about 2,000 feet (600 meters). Many wells are much deeper, and are measured in terms of miles. Moreover, as the steam cools and becomes water, the crude returns to its original highly viscous state, complicated by the material being a water-oil emulsion from which the desired petroleum products are hard to separate and refine.
Alternate heat recovery methods have been developed to overcome some the deficiencies of the steam injection methods. These include: the use of gas-fired radiant tube heaters located at the well bottom to heat the oil-bearing formation; the use of heated organic vapor in place of steam to heat the formation; and in situ exothermic reactions (i.e., alkali metals and water).
An alternative technique is to reduce viscosity by diluting the crude with less viscous hydrocarbons such as condensates, naphtha, or other solvents. Pipeline transportation usually requires blending the crude with lighter hydrocarbon diluents to obtain a kinematic viscosity of 1000 cps or less; however, supplies of diluent are insufficient to meet projected requirements.
Other chemical means for reducing HCO viscosity in oil-bearing formations include the use of solvents and surfactant systems, certain high molecular weight polymers and polysaccharide solutions. See for example, US 4,687,586 (Argabright et al.), US 4,425,246 (Holzwarth et al.), US 4,192,755 (Flournoy et aL) and US
BACKGROUI~TD OF THE INVENTION
The present invention relates generally to the field of petroleum production and transportation. In particular, the present invention relates to the use of certain amine-chelate complexes to reduce significantly the viscosity of heavy crude oils.
Heavy crude oils ("HCO" or "HCOs") constitute a significant portion of the known global petroleum reserves. Vast deposits of HCOs are located in Colombia, Venezuela, Mexico and Canada. HCOs are highly viscous or solid at ambient temperature, and have a gravity of 20 or less on the API (American Petroleum Institute) density scale. HCOs include the high molecular weight hydrocarbons referred to as "tars," "petroleum tars" or "tar sands," such as the deposit known as the Athabasca Tar Sands in Alberta, Canada. In comparison, "conventional" or "light" crudes such as those found in the Middle East typically have API
gravity of 37 or greater.
In addition to being more viscous than conventional crude oils, certain HCOs are rich in asphaltenes, metals and resins. While there is a wide variety in HCO
composition and physical properties, many HCOs typically contain high levels of sulfur, nitrogen, nickel and vanadium, and are rich in the condensed polyaromatic compounds which react readily to form coke. The presence of these types of compounds in HCOs can lead to various problems in the recovery, transportation, treatment and refining of crude oils.
In order for the extraction and transportation of HCOs to be economically viable, the flow resistance of the HCO must be reduced sufficiently to enable the use of reasonably sized wellbores, pipelines and pumping equipment. Some common methods of reducing flow resistance include: heat, dilution, partial field upgrading, water-emulsification, and lubrication and core-annular flow. Heat is generally applied using steam generated at or near the well site.
The primary method for recovering HCOs from oil-bearing formations is steam injection, also know as steam flooding. Although there are numerous variations, there are two basic techniques: the "huff and puff" (or "push-pull") involves injecting steam into a formation, alternating with back-producing the oil through the same well; and the "steam drive" involves injecting steam into a formation through one well (an "injection' well) and producing the oil from a different well (a "production' or "recovery" well). Variations include the number and type of wells, as well as their location and configuration.
The steam injection method is useful in recovery of HCOs because relatively small increases in the temperature of HCOs result in relatively large reductions in viscosity. This also explains some of the limitations and problems of this method.
For example, it is expensive but necessary to locate steam generators near the injection wells. In addition, heating of the oil-bearing formation also results in heating of the adjacent rock. Third, there is a lower limit to the well depth to which the steam injection can be effectively applied, since the steam cools and liquefies as it proceeds down the well-bore. This well depth limit will depend on the particular conditions at the well site, but will generally be about 2,000 feet (600 meters). Many wells are much deeper, and are measured in terms of miles. Moreover, as the steam cools and becomes water, the crude returns to its original highly viscous state, complicated by the material being a water-oil emulsion from which the desired petroleum products are hard to separate and refine.
Alternate heat recovery methods have been developed to overcome some the deficiencies of the steam injection methods. These include: the use of gas-fired radiant tube heaters located at the well bottom to heat the oil-bearing formation; the use of heated organic vapor in place of steam to heat the formation; and in situ exothermic reactions (i.e., alkali metals and water).
An alternative technique is to reduce viscosity by diluting the crude with less viscous hydrocarbons such as condensates, naphtha, or other solvents. Pipeline transportation usually requires blending the crude with lighter hydrocarbon diluents to obtain a kinematic viscosity of 1000 cps or less; however, supplies of diluent are insufficient to meet projected requirements.
Other chemical means for reducing HCO viscosity in oil-bearing formations include the use of solvents and surfactant systems, certain high molecular weight polymers and polysaccharide solutions. See for example, US 4,687,586 (Argabright et al.), US 4,425,246 (Holzwarth et al.), US 4,192,755 (Flournoy et aL) and US
3,964,548 (Schroeder Jr, et al.). The main problem with these chemical methods is the large volume of solvent needed (generally about 10-20% by volume of HCO).
In similar vein, US 5,876,018 (Karydas) discloses the use of certain fluorochemical compounds having oleophobic and hydrophobic groups to reduce the viscosity of asphaltenic crude oils, optionally in combination with a lvw viscosity diluent.
In spite of these and numerous other methods, high viscosity and the resultant lack of flow remains problematic in the recovery of HCOs. Moreover, many of these methods are ineffective in extracting petroleum from tar sands.
Last, even if the HCO can be extracted from the formation, transportation of the HCO
from the well site to the refinery or to storage is often difficult and expensive. The most prevalent form of transportation from the well site is by pipeline. With HCOs, the pipelines must be heated in order to maintain the flow of oil.
Thus, there remains a need for other HCO recovery methods, especially where the means of extraction can also be used to facilitate transportation of the material from the well site.
STATEMENT OF THE INVENTION
The present invention is directed to novel amine-chelate complexes formed by heating together at least one organic amine; and at least one chelating agent.
The present invention also includes compositions for reducing the viscosity of heavy crude oils, comprising 0.01- 50 wt% of at least one such amine-chelate complex and an organic solvent.
The present invention is also directed to a method for recovering. heavy crude oil from an oil-bearing formation having at least one well penetrating said formation and in fluid communication therewith, comprising the steps of: (a) injecting into the well and the formation a viscosity-reducing amount of an amine-chelate complex as described above; (b) allowing the amine-chelate complex to disperse into the formation; and (c) recovering the reduced viscosity oil.
In yet another aspect, the present invention is also.directed to a method for reducing viscosity of heavy crude oils in significantly non-reversible manner, .
comprising the steps of: adding a viscosity-reducing amount of an amine-chelate complex of the present invention to a heavy crude oil, and dispersing the amine-chelate complex throughout a portion of the heavy crude oil.
DETAILED DESCRIPTION OF THE INVENTION
As used in this specification, the terms "crude" and "crude oil" are used interchangeably, and refer to unrefined petroleum. The following abbreviations are used throughout this specification: mL = milliliter; m = meter; km =
kilometer; g =
grams; wt% = percent by weight; pprn = parts per million; rpm = revolutions per minute; cps = centipoise; HOAc = acetic acid; EDTA = ethylenediamine tetraacetic acid; NTA = nitrilotriacetic acid. Unless otherwise indicated, all ranges (including ranges of xatios) are inclusive. \
The complexes of the present invention are generally formed by heating certain organic amines ~n,~ith certain chelating agents. The amounts of amine and chelating agent used to form the complexes can vary greatly, depending on several factors such as the particular application, the HCO composition, and the physical properties of the HCO and the formation from which it is to be extracted;
however, in general the molar equivalent ratio of amine to chelating agent acid equivalent will be in the range of 10:1 to 1:2. It is preferred that the ratio is 6:1 to 1:1.
Most preferred is a ratio of 5:1 to 4.5:1.
Combinations of different complexes of the present invention can also be used. Combinations can be prepared either by mixing different amines, chelating agents, or both, to form mixtures of the complexes, or by mixing different complexes prepared separately.
For HCO recovery, the complexes of the present invention can be injected directly into an injection well, or are preferably diluted with solvent prior to injection. Suitable solvents include but are not limited to: petroleum distillates such as kerosene and gas oil; linear and branched aliphatic solvents such as pentane, hexane, mixtures of nonanes and 2-ethylhexanes; cycloaliphatic mixtures commonly known as naphtha; aromatic solvents such as toluene, xylenes and commercial solvent mixtures such as aromatic solvents 100,150 and 200; esters; ethers;
alcohols such as ethanol, isopropanol, octanol and dodecanol; ketones such as acetone, cyclohexanone and acetophenone; and other polar solvents. Typical dilutions are 0.01 to 50 wt% of the complex, with preferred dilutions being 0.01 to IO wt%.
The complexes of the present invention can also be used in conjunction with other recovery methods, such as steam injection or organic vapor injection (e.g., US
4,407,367 (Kydd) or US 5,143,156 (Bromley)).
The amount of complex used to lower viscosity for HCO recovery or transportation will vary greatly depending on the amount of viscosity reduction desired, and whether or not additional recovery means will be used. HCO
viscosity varies dramatically with increasing amounts of the complexes of the present invention.
Depending on the method of recovery, it may also be useful to add the complexes of the present invention once the oil has been brought to the surface, in order to facilitate transportation of the oil from the well site. If additional complexes are desired, such complexes can be added in the recovery well, or at any time thereafter.
The amines useful to make the complexes of the present invention are organic amines, preferably primary amines. As used in this specification, the term "amine"
is used to describe both monoamines and polyamines. It is preferred to use oil-soluble amines to prepare the complexes of the present invention.
In similar vein, US 5,876,018 (Karydas) discloses the use of certain fluorochemical compounds having oleophobic and hydrophobic groups to reduce the viscosity of asphaltenic crude oils, optionally in combination with a lvw viscosity diluent.
In spite of these and numerous other methods, high viscosity and the resultant lack of flow remains problematic in the recovery of HCOs. Moreover, many of these methods are ineffective in extracting petroleum from tar sands.
Last, even if the HCO can be extracted from the formation, transportation of the HCO
from the well site to the refinery or to storage is often difficult and expensive. The most prevalent form of transportation from the well site is by pipeline. With HCOs, the pipelines must be heated in order to maintain the flow of oil.
Thus, there remains a need for other HCO recovery methods, especially where the means of extraction can also be used to facilitate transportation of the material from the well site.
STATEMENT OF THE INVENTION
The present invention is directed to novel amine-chelate complexes formed by heating together at least one organic amine; and at least one chelating agent.
The present invention also includes compositions for reducing the viscosity of heavy crude oils, comprising 0.01- 50 wt% of at least one such amine-chelate complex and an organic solvent.
The present invention is also directed to a method for recovering. heavy crude oil from an oil-bearing formation having at least one well penetrating said formation and in fluid communication therewith, comprising the steps of: (a) injecting into the well and the formation a viscosity-reducing amount of an amine-chelate complex as described above; (b) allowing the amine-chelate complex to disperse into the formation; and (c) recovering the reduced viscosity oil.
In yet another aspect, the present invention is also.directed to a method for reducing viscosity of heavy crude oils in significantly non-reversible manner, .
comprising the steps of: adding a viscosity-reducing amount of an amine-chelate complex of the present invention to a heavy crude oil, and dispersing the amine-chelate complex throughout a portion of the heavy crude oil.
DETAILED DESCRIPTION OF THE INVENTION
As used in this specification, the terms "crude" and "crude oil" are used interchangeably, and refer to unrefined petroleum. The following abbreviations are used throughout this specification: mL = milliliter; m = meter; km =
kilometer; g =
grams; wt% = percent by weight; pprn = parts per million; rpm = revolutions per minute; cps = centipoise; HOAc = acetic acid; EDTA = ethylenediamine tetraacetic acid; NTA = nitrilotriacetic acid. Unless otherwise indicated, all ranges (including ranges of xatios) are inclusive. \
The complexes of the present invention are generally formed by heating certain organic amines ~n,~ith certain chelating agents. The amounts of amine and chelating agent used to form the complexes can vary greatly, depending on several factors such as the particular application, the HCO composition, and the physical properties of the HCO and the formation from which it is to be extracted;
however, in general the molar equivalent ratio of amine to chelating agent acid equivalent will be in the range of 10:1 to 1:2. It is preferred that the ratio is 6:1 to 1:1.
Most preferred is a ratio of 5:1 to 4.5:1.
Combinations of different complexes of the present invention can also be used. Combinations can be prepared either by mixing different amines, chelating agents, or both, to form mixtures of the complexes, or by mixing different complexes prepared separately.
For HCO recovery, the complexes of the present invention can be injected directly into an injection well, or are preferably diluted with solvent prior to injection. Suitable solvents include but are not limited to: petroleum distillates such as kerosene and gas oil; linear and branched aliphatic solvents such as pentane, hexane, mixtures of nonanes and 2-ethylhexanes; cycloaliphatic mixtures commonly known as naphtha; aromatic solvents such as toluene, xylenes and commercial solvent mixtures such as aromatic solvents 100,150 and 200; esters; ethers;
alcohols such as ethanol, isopropanol, octanol and dodecanol; ketones such as acetone, cyclohexanone and acetophenone; and other polar solvents. Typical dilutions are 0.01 to 50 wt% of the complex, with preferred dilutions being 0.01 to IO wt%.
The complexes of the present invention can also be used in conjunction with other recovery methods, such as steam injection or organic vapor injection (e.g., US
4,407,367 (Kydd) or US 5,143,156 (Bromley)).
The amount of complex used to lower viscosity for HCO recovery or transportation will vary greatly depending on the amount of viscosity reduction desired, and whether or not additional recovery means will be used. HCO
viscosity varies dramatically with increasing amounts of the complexes of the present invention.
Depending on the method of recovery, it may also be useful to add the complexes of the present invention once the oil has been brought to the surface, in order to facilitate transportation of the oil from the well site. If additional complexes are desired, such complexes can be added in the recovery well, or at any time thereafter.
The amines useful to make the complexes of the present invention are organic amines, preferably primary amines. As used in this specification, the term "amine"
is used to describe both monoamines and polyamines. It is preferred to use oil-soluble amines to prepare the complexes of the present invention.
Generally speaking, the preferred amines are aliphatic primary monoamines, having the general formula (I):
R-NHz (I) Especially preferred are: saturated or olefinically unsaturated aliphatic primary amines such as n-octylamine, 2-ethylhexylamine, t-octylamine, n-decylam.ine, Coo tertiary alkyl primary amines (either singly or in any combinations thereof), tridecylamine, n-undecylamine, lauryl amine, hexadecylamine, heptadecylamine, octadecylamine, decenylamine, dodecenylamine, palmitoleylamine, oleylamine, linoleylamine, eicosenylamine and polyetheramine; and polyalkylamines such as polyisobutyleneamine. Commercially available mixtures of suitable primary aliphatic amines in the C12 - CZS range include ARMEEN O and ARMEEN OD (Akzo Nobel; Stratford, CT).
It is preferred to use oil-soluble aliphatic amines in which the aliphatic group is a tertiary aliphatic group, most preferably a tertiary alkyl group.
Commercially available mixtures of suitable amines of this type include PRIMENE TOA, PRIMENE
BC-9; PRIMENE 81-R and PRIMENE JM-T amines (Rohm and Haas Company;
Philadelphia, PA).
Also desirable are the saturated or substantially saturated aliphatic (Ca -C4o) secondary amines, such as diethanolamine, morpholine, di-isoamylamine, di-n-octylamine, di-(2-ethylhexyl)amine, di(cyclohexyl)amine, di-(t-octyl)amine, di-n-nonylamine, dilauryl amine, di-hexadecylamine, di-octadecylamine, and di-oleylamine. One such commercially available secondary amine is the long chain alkylamine known as AMBERLITE LA-2 (Rohm and Haas Company).
Also desirable are tertiary monoamines exemplified by cyclohexyl dimethyl amine, triethanolamine, pyridine and trioctyl amine.
A few representative examples of polyamine reactants which may be employed in this invention include straight or branched-chain alkanes containing two or more amino groups, at least one of which is a primary amino group. Such compounds include but are not limited to: polyaminoalkanes such as 1,6-diaminooctane,1,8-diaminooctane,1,5,9-triaminononane and tetraamino- ' neopentane; polyaminoalkanols such as 2-(2-aminoethylamino)ethanol and 2-[2-(2-aminoethylamino)ethylarnino]ethanol; heterocyclic compounds containing two or more amino groups at least one of which is a primary amino group, such as 1-((3-aminoethyl)-2-imidazolidone, 2-(2-aminoethylarnino)-5-nitropyridine, 3-amino-N-ethylpiperidine, 2-(2-aminoethyl)-pyridine, 5-aminoindole, 3-amino-5-mercapto-1,2,4-triazole, 4-(aminomethyl)piperidine, 3-aminopiperidine and 2-aminopyridine;
alkylene polyamines such as 1,2-propylene diamine, di-(1,2-propylene)triamine, di-(1,3-propylene)triamine, N,N-dimethyl-1,3-propanediam.ine,1,4-butanediamine, di-(I,2-butylene)triamine, N-(2-aminoethyl)-1,3-propanediamine, hexamethylenediamine and tetra-(1,2-propylene)pentamine; hydroxyamines such as tris(hydroxyrnethyl)aminomethane, isopropanol amine, N-(2-hydroxyethyl)-1,3-propanediamine, N-2-hydroxypropylethylene diamine, N-aminoethylethanolamine and 4-aminophenol; aromatic polyamines such as p-phenylene diamine and the like;
N,N'-disalicylidene-1,2-alkane diamines such as N,N'disalicylidene-1,2-ethane dianune, N,N'disalicylidene-1,2-butane diamine, N,N'disalicylidene-1,2-cyclohexane diamine and (most preferably) N,N'-disalicylidene-1,2-propane diamine. Also preferred are PRIMENE MD (Rohm and Haas Company) and isophorone diamine.
Other useful polyamines include polyoxyalkylene polyamines such as the polyoxyalkylene diamines and polyoxyalkylene triamines, which may have various number average molecular weights, typically in the range of about 200 to about 4,000. Polyoxyalkylene polyamines are commercially available, and may be obtained for example, from Huntsman Chemical Company, Inc. (Conroe, TX), under the JEFFAMINE trademarks (e.g., JEFFAMINE D-230, JEFFAMINE D-400, JEFFAMINE D-1000, JEFFAMINE D2000, JEFFAMINE T-403).
Another group of polyoxyalkylene polyamines are those represented by formula (II):
R-C(O)-C(R)H-CH2-C(O)-R (II) -wherein R = - NH - (alkylene-O)nalkylene-NHZ and n = 2 or 3. The alkylene groups can be the same or different and are straight or branched chain groups containing 2 to 8 carbon atoms each, preferably 2 to 4 carbon atoms each. These compounds are formed by reacting 3 to about 3.5 moles of a dicarboxylic acid reactant such as malefic acid, fumaric acid, their anhydrides or Cl.~ dialkyl esters with a polyoxyalkylene diamine of the formula HZN-(alkylene-O)n-alkylene-NH2, wherein the alkylene and n are as defined above.
The alkylene polyamine reactants which are useful with tlus invention include polyamines which are linear, branched, cyclic or mixtures thereof, wherein each alkylene group contains 1 to 10 carbon atoms. In this class of amines are the ethylene poly~.mines which can be depicted by formula (III):
H2N(CH2CH2NH)~H (III) wherein n is an integer from one to about ten.
Preferred ethylene polyamines acre polyamines containing 2 to 10 nitrogen 25 atoms per molecule or a mixture of polyamines containing an average of 2 to nitrogen atoms per molecule. These compounds include but are not limited to:
ethylenediamine, diethylene triamine, triethylene tetramine, tetraethylene pentamine, pentaethylene hexamine, hexaethylene heptarnine, heptaethylene octamine, octaethylene nonarnine, nonaethylene decamine and mixtures thereof.
Corresponding propylene polyamines such as propylene diamirte, dipropylene triamine, tripropylene tetrarnine, tetrapropylene pentamine and pentapropylene hexamine are also suitable amine reactants. Particularly preferred polyamines are polyamine or mixture of polyamines having an average of 3 to 7 nitrogen atoms in combination with diethylene triamine, or mixtures of ethylene polyamines whose physical and chemical properties approximate that of diethylene triamine. In selecting an appropriate polyamine, consideration should be given to its solubility in HCOs.
-g_ Commercially available ethylene polyamine mixtures usually contain minor amounts of branched species and cyclic species such as N-amino-ethyl piperazine, N,N'-bis(aminoethyl)piperazine, N,N'-bis(piperazinyl)ethane and like compounds.
The preferred commercial mixtures have a approximate overall compositions falling ' in the range corresponding to diethylene triamine to pentaethylene hexamine, mixtures generally corresponding in overall makeup to tetraethylene pentamine being most preferred. Various suitable low cost polyethylene polyamine mixtures are available.under various trade designations such as POLYAMINE H, POLYAMINE 400, DOW POLYAMINEE-100, and DOW S-1107 (Dow Chemicals,;
Midland, MI) .
A most preferred class of amines. useful in the present invention are tertiary alkyl primary amines of formula (IV):
R~-NHZ (~) wherein R1, R2, and R3 are each independently selected from: (Cl-C3~) alkyl;
substituted (Cl-Cs~) alkyl; (Cl-Cap) alkenyl; and substituted (Ci-Cap) alkenyl. As used in this specification, the term "(Cl-C3~)" means a straight chain or branched alkyl or alkenyl group having 1 to 37 carbon atoms per group.
Suitable examples of (Ci-C3~) alkyl include, but are not limited to: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, 2-ethylhexyl, octyl, decyl, isodecyl, undecyl, dodecyl (also known as lauryl), tridecyl, tetradecyl (also known as myristyl), pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, cosyl and eicosyl.
Suitable examples of (Ci-C3~) alkenyl include, but are not limited to:
ethenyl, n-propenyl, isopropenyl,1-butenyl, cis-2-butenyl, isobutylene, traps-2-butenyl, 2,3,-dimethyl-2-butenyl, 3-methyl-1-butenyl, 2-methyl-2-butene,1-pentenyl, cis-pentenyl, traps-2-pentenyl,1-hexenyl,1-heptenyl,1-octenyl,1-nonenyl and 1-decenyl.
Suitable examples of (CI-C37) substituted alkyl and alkenyl include, but are not limited to the above recited alkyl and alkenyl groups substituted with:
hydroxy;
halide such as fluorine, chlorine or bromine; cyano; alkoxy; haloalkyl;
carbalkoxy;
carboxy; amino; alkylamino derivatives and the like; and vitro groups.
These tertiary alkyl primary amines rriay be used as a single amine or a mixture of amines, and include but are not limited to: 1,1,3,3-tetramethylbutylamine (PRIMENE TOA); an isomeric mixture of Cib to C~ tertiary alkyl primary amines (PRIMENE JM-T); an isomeric mixture of Cs to Cio tertiary alkyl primary amines (PRIMENE BC-9); an isomeric mixture of Ci2 to Ci4 tertiary alkyl primary amines (PRIMENE 81-R); or mixtures thereof. It is preferred to use PRIMENE BC-9, PRIMFNE 81-R, or mixtures thereof. Most preferred is PRIIIrtENE BC-9.
A chelating agent, or chelant, is a compound which contains two or more electron donor atoms that can form coordinate bonds to a single metal atom. A
chelate compound may be either a neutral molecule or complex ion associated with the appropriate counterion. Chelating agents may be either organic or inorganic, aromatic or aliphatic, linear or cyclic, branched or linear aliphatic. A
broader discussion of chelating agents can be found in an article by W. L. Howard and D. A.
Wilson in Kroschwitz, J. I. (Ed.), Kirk-Othmer Enc~cla, ep dia Of Chemical Teclznotogy, Volume 5, 4~ Edition, J. Wiley: NY (1993), pp. 764-795. For purposes of this invention, those chelants that can form oil soluble complexes with said amines are preferred.
Some of the preferred classes of chelating agents useful in the present invention include: organic acids such as acetic acid, acrylic acid and lauric acid;
arninocarboxylic acids such as ethylenediaminetetraacetic acid, hydroxyethyl-ethylenediaminetriacetic acid, nitrilotriacetic acid, N-dihydroxyethylglycine and ethylenebishydroxyphenyglycine; phosphoric acids such as nitrilotrimethylene-phosphoruc acid, ethylenediaminetetra(methylenephosphonic acid) and hydroxyethylidenediphosphonic acid; polyphosphates such as sodium tripolyphosphate and hexametaphosphoric acid;1,3-diketones such as acetylacetone, trifluoroacetylacetone and thenoyltrifluoroacetone; phenols such as salicylaldehyde, disulfopyrocatechol and chromotropic acid; aminophenols such as oxine, 8-hydroxyquinoline and oxinesulforic acid; oximes such as dimethylglyoxime and salicylaldoxime; sulfur compounds.such as thioglycolic acid and diethyl dithiophosphoric acid; macrocylic compounds such as dibenzo-[18]-crown-6, hexamethyl-[14]-4,11-dieneN4 and (2.2.2-cryptate); polycarboxylic acids such as citric acid and polyp-vinylbenzyliminodiacetic acid); terminally unsaturated acrylic acid oligomers such as described in US 5,710,227 (Freemand et al:); other polymeric compounds such as polymethacryloylacetone; and salts of such compounds, as appropriate. It is most preferred to use ~iOAc, EDTA, NTA and their salts.
Most preferred are EDTA and its salts.
The following examples are presented to illustrate further various aspects of the present invention, but are not intended to limit the scope of the invention in any respect.
Examples 1-11 illustrate the prepaxation of various complexes of the present invention.
Example 1 To a 3-necked round bottom flask equipped with a rnecharucal stirrer, heating mantle, addition funnel and reflux condenser was added 0.5 moles of an isomeric mixture of Ciz to Ci4 tertiary alkyl primary amines. The mixture was heated to about 60 °C, at which time 0.2 moles of EDTA was slowly added to the amine mixture through the additional funnel, with stirring, to maintain the temperature between 80 and 100 °C. When addition was completed, the reaction temperature was raised to 120-140 °C and maintained for about an hour (or until the EDTA was completely dissolved). The pH of the mixture was checked, and if below 8.5, additional amine was added. The reaction mixture was then allowed to cool to room temperature.
Example 2 To a 3-necked round bottom flask equipped with a mechanical stirrer, heating mantle, addition funnel and reflux condenser was added 0.26 moles of an isomeric mixture of Ci2 to Cia tertiary alkyl primary amines and 113 g of toluene. The mixture was heated to about 60 °C, at which time 0.057 moles of EDTA
was slowly added to the amine and toluene mixture through the additional funnel, with stirring, to maintain the temperature between 80 and 100 °C. When addition was completed, the reaction temperature was maintained at 100 °C for about four hours (or until the EDTA was completely dissolved). The pH of the mixture was checked, and if below 8.5, additional amine was added. The reaction mixture was then allowed to cool to room temperature. .
Example 3 To a 3-necked round bottom flask equipped with a mechanical stirrer, heating mantle, addition funnel and reflux condenser was added 0.9 moles of an isomeric mixture of Cs to Cio tertiary alkyl primary amines. The mixture was heated to about 60 °C, at which time 0.05 moles of EDTA was slowly added to the amine and toluene mixture through the additional funnel, with stirring, to maintain the temperature between 80 and 100 °C. When addition was completed, the reaction temperature 15~ was maintained at 100 °C for about four hours. The pH of the mixture was checked, and if below 8:5, additional amine was added. The reaction mixture was then allowed to cool to room temperature.
Example 4 To a 3-necked round bottom flask equipped with a mechanical stirrer, heating mantle; addition funnel and reflux condenser was added 0.26 moles of an isomeric mixture of Cs to Cio tertiary alkyl primary amines and 103 g of kerosene. The mixture was heated to about 60 °C, at which time 0.02 moles of NTA was slowly added to the amine and toluene mixture through the additional funnel, with stirnng, to maintain the temperature between 80 and 100 °C. When addition was completed, the reaction temperature was maintained at 100 °C for about four hours.
The pH of the mixture was checked, and if below 8.5, additional amine was added. The reaction mixture was then allowed to cool to room temperature.
Example 5 To a 3-necked round bottom flask equipped with a mechanical stirrer, heating mantle, addition funnel and reflux condenser was added 0.3 moles of an isomeric mixture of Clo to C14 tertiary alkyl primary amines and 103 g of kerosene. The mixture was heated to about 60 °C, at which time 0.02 moles of NTA was slowly added to the amine and toluene mixture through the additional funnel, with stirring, to maintain the temperature between 80 and 100 °C. ~Nhen addition was completed, the reaction temperature was maintained at 100 °C for about four hours.
The pH of the mixture was checked, and if below 8.5, additional amine was added. The reaction mixture was then allowed to cool to room temperature.
Example 6 To a 3-necked round bottom flask equipped with a mechanical stirrer, heating mantle; addition funnel and reflux condenser was added 85.9 g of Example 3 and 38.8 g of Cs to Cio tertiary alkyl prunary amines. The mixture was heated to about 100 °C for an hour or until the mixture was clear. The reaction mixture was then allowed to cool to room temperature.
Example 7 To a 3-necked round bottom flask equipped with a mechanical stirrer, heating mantle, addition funnel and reflux condenser was added 40 g of the mixture from Example 6 and 40 g of toluene. The mixture was mixed until homogeneous and clear.
Example 8 To the material from Example 4, 59 g of isopropanol was added and mixed until the material was clear.
Example 9 To a 3-necked round bottom flask equipped with a mechanical stirrer, heating mantle, addition funnel and reflux condenser was added 0.34 moles of an isomeric mixture of Cib to C~ tertiary alkyl primary amines. The mixture was heated to about 60 °C, at which time 0.12 moles of acetic acid was slowly added to the amine mixture through the additional funnel, with stirring, to maintain the temperature between 80 and 100 °C. When addition was completed, the reaction temperature was raised to 120-140 °C and maintained for about an hour (or until the mixture was completely clear). The pH of the mixture was checked, and if below 8.5, additional arriine was added. The reaction mixture was then allowed to cool to room temperature.
Example 10 To a 3-necked round bottom flask equipped with a mechanical stirrer, Beating mantle, addition funnel and reflux condenser was added 0.33 moles of an isomeric mixture of Cib to Czz tertiary allcyl primary amines. The mixture was heated to about 60 °C, at which time 0.05 moles of citric acid was slowly added to the amine mixture through the additional funnel, with stirring, to maintain the temperature between 80 and 100 °C. When addition was completed, the reaction temperature was raised to 120-140 °C and maintained for about an hour (or until the citric acid was completely dissolved). The pH of the mixture was checked, and if below 8.5, additional amine was added. The reaction mixture was then allowed to cool to room temperature.
Facam~le 11 To a 3-necked round bottom flask equipped with a mechanical stirrer, heating mantle, addition funnel and reflux condenser is added 0.9 moles of AMBERLITE
LA-2. The mixture was heated to about 60 °C, at which time 0.1 moles of nitrilotrimethylene-phosphoric acid is slowly added to the amine mixture through the additional funnel, with stirnng, to maintain the temperature between 80 and 100 °C. When addition is completed, the reaction temperature is raised to 120 -140 °C
and maintained for about an hour (or until the mixture is clear). The pH of the mixture is checked, and if below 8.5, additional AMBERLITE LA-2 is added. The reaction mixture is then allowed to cool to room temperature.
In the following Examples 12-16, the viscosity measurements were made using a Brookfield viscometer Model DV-III equipped with a THERMOSEL system - i4 -i (Brookfield Engineering Laboratories, Inc., Stoughton, MA) and a temperature controller with an RTD (remote temperature detector) probe. The THERMOSEL
system consists of a heating chamber, a removable sample chamber, an SC4.spindle and an insulating cap. As the THERMOSEL system requires only 8 mL of sample, the sample temperature is readily controlled and the viscosity is more accurately measurable Example 12 This Example illustrates the effect of complex concentration on the viscosity of Venezuelan Heavy Crude Oil. In this Example, the additive was the complex of Example 1.
Sample Additive Temp = 75 F (24 C) Temg. =150 F (66 C) ID (ppm) Viscosity cps)% ReductionViscosity % Reduction (cps) 750 3000 25.0 250 19.9 1000 2950 26.2 242 22.4 1250 2850 28.8 235 24.7 1750 2650 33.8 212 32.0' _ _2_000 ___2350__ _4_1.2 ___ 207 __3_3.6 _ _ 0 56000 - 2050 _ 750 38000 32.1 1700 17.1 1000 32000 42.8 1600 22.0 1250 27500 50.1 1500 26.8 1750 24500 56.2 1350 34.1 2000 23500 _ 58.0 1250 _ 39.0 -- - -- --- ---. 1-C 0 __ 7900 --750 --- --- 6200 21.5 1000 - - 6150 22.2 1250 - - 6000 24.0 1750 ~ - - 4600 41.8 _ _2_000 ___ -_ ___-- __ 3800_ __5_1.9 -__ _ 750 83000 2.4 2900 23.7 1000 70500. 17.0 2500 34.2 1250 58000 31.8 2400' 36.8 1750 51000 40.0 2300 39.5 2000 42500 50.0 1750 53.9 I
Example 13 This Example further illustrates the effect of complex concentration on the viscosity of Venezuelan Heavy Crude Oil. In this Example, the additive was the complex of Example 1.
Sample Additive Tem~,=110 F X43 C~ Temp =120 F (49 C~
ID . (ppm) Viscosity % ReductionViscosity % Reduction (cps) (cps) 500 38000 20.0 20000 25.9 1000 30000 36.8 16500 38.9 1500 22000 53:7 11500 57.4 ___ _2_000 _ _17500 ___63.2 ___8000 _ 70.4__ 1-F 0 _ - _ 500 9004 15.1 5800 10.8 1000 7500 29.2 5100 21.5 1500 6900 35.0 4800 26.2 2000 5900_ 44.3 4200_ 35.4 -- --- -- --- --~--_ 500 950 2.6 675 10.6 1000 725 25.6 550 27.2 1500 625 35.9 460 39.1 ___ _2_000 ___ 600_ ___38.5 _ 425_ __4_3.7__ -500 3000 11.8 ~ 2350 14.5 1000 2550 25.0 1950 29.1 1500 2200 35.3 1600 41.8 2000 1950 42.6 1400 49.1 Example 14 This Example illustrates the effect of complex concentration on the viscosity of pipeline HCO at various temperatures. In this Example, the adclitive was the complex of Example 1.
Temp. (°F/°C) Additive (ppm) Viscosity (cps) % Reduction 75/ 24 0 ' 6580 --750 5650 17.5 1000 5450 20.4 1250 5200 ~ 24.1 1750 4500 34.3 I
._ - 90/32 -- - - 0 - - - ~~_. - - - _ 750 2312 19.3 1000 2125 25.8 1250 1875 34.6 ____ __ 175_0 __ 14_62_ _ 4_9.0 ~ - !
__ 492 -750 440 10.6 1000 420 ~ 14.6 1250 390 20.7 1750 340 30.9 Examyle 15 This Example further illustrates the effect of complex concentration on the viscosity of flow station HCO at various temperatures. In the Table below, the Sample ID numbers correspond to Example numbers. For example, 9 means that the additive was the complex of Example 9.
Sample Additive Temp = 75 F 24 C) Temp =15U
~ F f66 C1 ID (ppm) Viscosity (cps)% ReductionViscosity % Reduction (cps) C_ont_rol_ _ 0 _ _ 1280_0 _- _ _ _ 825_ _ _ _- _ ~ _ --_ 750 10000 21.9 680 17.6 1000 10600 17.2 665 19.4 1250 9000 29.7 640 22.4 _1500 _ _ _ 880_0 _ _31.2 _ _ 630_ _ _23.6 _ _ -_ _ ! 750 8300 35.2 ~ 710 13.9 1000 8400 34.4 670 18.8 1250 9600 25.0 550 33.3 1500 ___ 640_0 __50.0 __ 560_ __32.1 _ i ___ __ 10800 15.6 _ _ 17 750 800 3.0 1000 10600 17.2 650 21.2 1250 9000 29.7 655 _ . 20.6 1500 10000 21.9 540 - 34.5 Example 16 This example further demonstrates that the viscosity reduction obtained by addition of the complexes of the present invention to samples of Venezuelan HCO is not affected by different diluents.
Additive A-3 was made by diluting the complex of Example 3 with toluene, and Additive B-4 was made by diluting the complex of Example 4 with kerosene.
Both complexes were diluted to 10% active.
Additive Temperature Viscosity (cps)% Reduction (C) None 21 118655 ____ 40 3_1253 --- - - - - , - - - - - -2000 ppm (A-3)21 82182 30.7 _ _ _ _ _ 40 8432 73.0 _ _ - - -- . -r - - - - -- -2000 ppm (B-4)21 73304 38.2 - ~
40 7507 76.0
R-NHz (I) Especially preferred are: saturated or olefinically unsaturated aliphatic primary amines such as n-octylamine, 2-ethylhexylamine, t-octylamine, n-decylam.ine, Coo tertiary alkyl primary amines (either singly or in any combinations thereof), tridecylamine, n-undecylamine, lauryl amine, hexadecylamine, heptadecylamine, octadecylamine, decenylamine, dodecenylamine, palmitoleylamine, oleylamine, linoleylamine, eicosenylamine and polyetheramine; and polyalkylamines such as polyisobutyleneamine. Commercially available mixtures of suitable primary aliphatic amines in the C12 - CZS range include ARMEEN O and ARMEEN OD (Akzo Nobel; Stratford, CT).
It is preferred to use oil-soluble aliphatic amines in which the aliphatic group is a tertiary aliphatic group, most preferably a tertiary alkyl group.
Commercially available mixtures of suitable amines of this type include PRIMENE TOA, PRIMENE
BC-9; PRIMENE 81-R and PRIMENE JM-T amines (Rohm and Haas Company;
Philadelphia, PA).
Also desirable are the saturated or substantially saturated aliphatic (Ca -C4o) secondary amines, such as diethanolamine, morpholine, di-isoamylamine, di-n-octylamine, di-(2-ethylhexyl)amine, di(cyclohexyl)amine, di-(t-octyl)amine, di-n-nonylamine, dilauryl amine, di-hexadecylamine, di-octadecylamine, and di-oleylamine. One such commercially available secondary amine is the long chain alkylamine known as AMBERLITE LA-2 (Rohm and Haas Company).
Also desirable are tertiary monoamines exemplified by cyclohexyl dimethyl amine, triethanolamine, pyridine and trioctyl amine.
A few representative examples of polyamine reactants which may be employed in this invention include straight or branched-chain alkanes containing two or more amino groups, at least one of which is a primary amino group. Such compounds include but are not limited to: polyaminoalkanes such as 1,6-diaminooctane,1,8-diaminooctane,1,5,9-triaminononane and tetraamino- ' neopentane; polyaminoalkanols such as 2-(2-aminoethylamino)ethanol and 2-[2-(2-aminoethylamino)ethylarnino]ethanol; heterocyclic compounds containing two or more amino groups at least one of which is a primary amino group, such as 1-((3-aminoethyl)-2-imidazolidone, 2-(2-aminoethylarnino)-5-nitropyridine, 3-amino-N-ethylpiperidine, 2-(2-aminoethyl)-pyridine, 5-aminoindole, 3-amino-5-mercapto-1,2,4-triazole, 4-(aminomethyl)piperidine, 3-aminopiperidine and 2-aminopyridine;
alkylene polyamines such as 1,2-propylene diamine, di-(1,2-propylene)triamine, di-(1,3-propylene)triamine, N,N-dimethyl-1,3-propanediam.ine,1,4-butanediamine, di-(I,2-butylene)triamine, N-(2-aminoethyl)-1,3-propanediamine, hexamethylenediamine and tetra-(1,2-propylene)pentamine; hydroxyamines such as tris(hydroxyrnethyl)aminomethane, isopropanol amine, N-(2-hydroxyethyl)-1,3-propanediamine, N-2-hydroxypropylethylene diamine, N-aminoethylethanolamine and 4-aminophenol; aromatic polyamines such as p-phenylene diamine and the like;
N,N'-disalicylidene-1,2-alkane diamines such as N,N'disalicylidene-1,2-ethane dianune, N,N'disalicylidene-1,2-butane diamine, N,N'disalicylidene-1,2-cyclohexane diamine and (most preferably) N,N'-disalicylidene-1,2-propane diamine. Also preferred are PRIMENE MD (Rohm and Haas Company) and isophorone diamine.
Other useful polyamines include polyoxyalkylene polyamines such as the polyoxyalkylene diamines and polyoxyalkylene triamines, which may have various number average molecular weights, typically in the range of about 200 to about 4,000. Polyoxyalkylene polyamines are commercially available, and may be obtained for example, from Huntsman Chemical Company, Inc. (Conroe, TX), under the JEFFAMINE trademarks (e.g., JEFFAMINE D-230, JEFFAMINE D-400, JEFFAMINE D-1000, JEFFAMINE D2000, JEFFAMINE T-403).
Another group of polyoxyalkylene polyamines are those represented by formula (II):
R-C(O)-C(R)H-CH2-C(O)-R (II) -wherein R = - NH - (alkylene-O)nalkylene-NHZ and n = 2 or 3. The alkylene groups can be the same or different and are straight or branched chain groups containing 2 to 8 carbon atoms each, preferably 2 to 4 carbon atoms each. These compounds are formed by reacting 3 to about 3.5 moles of a dicarboxylic acid reactant such as malefic acid, fumaric acid, their anhydrides or Cl.~ dialkyl esters with a polyoxyalkylene diamine of the formula HZN-(alkylene-O)n-alkylene-NH2, wherein the alkylene and n are as defined above.
The alkylene polyamine reactants which are useful with tlus invention include polyamines which are linear, branched, cyclic or mixtures thereof, wherein each alkylene group contains 1 to 10 carbon atoms. In this class of amines are the ethylene poly~.mines which can be depicted by formula (III):
H2N(CH2CH2NH)~H (III) wherein n is an integer from one to about ten.
Preferred ethylene polyamines acre polyamines containing 2 to 10 nitrogen 25 atoms per molecule or a mixture of polyamines containing an average of 2 to nitrogen atoms per molecule. These compounds include but are not limited to:
ethylenediamine, diethylene triamine, triethylene tetramine, tetraethylene pentamine, pentaethylene hexamine, hexaethylene heptarnine, heptaethylene octamine, octaethylene nonarnine, nonaethylene decamine and mixtures thereof.
Corresponding propylene polyamines such as propylene diamirte, dipropylene triamine, tripropylene tetrarnine, tetrapropylene pentamine and pentapropylene hexamine are also suitable amine reactants. Particularly preferred polyamines are polyamine or mixture of polyamines having an average of 3 to 7 nitrogen atoms in combination with diethylene triamine, or mixtures of ethylene polyamines whose physical and chemical properties approximate that of diethylene triamine. In selecting an appropriate polyamine, consideration should be given to its solubility in HCOs.
-g_ Commercially available ethylene polyamine mixtures usually contain minor amounts of branched species and cyclic species such as N-amino-ethyl piperazine, N,N'-bis(aminoethyl)piperazine, N,N'-bis(piperazinyl)ethane and like compounds.
The preferred commercial mixtures have a approximate overall compositions falling ' in the range corresponding to diethylene triamine to pentaethylene hexamine, mixtures generally corresponding in overall makeup to tetraethylene pentamine being most preferred. Various suitable low cost polyethylene polyamine mixtures are available.under various trade designations such as POLYAMINE H, POLYAMINE 400, DOW POLYAMINEE-100, and DOW S-1107 (Dow Chemicals,;
Midland, MI) .
A most preferred class of amines. useful in the present invention are tertiary alkyl primary amines of formula (IV):
R~-NHZ (~) wherein R1, R2, and R3 are each independently selected from: (Cl-C3~) alkyl;
substituted (Cl-Cs~) alkyl; (Cl-Cap) alkenyl; and substituted (Ci-Cap) alkenyl. As used in this specification, the term "(Cl-C3~)" means a straight chain or branched alkyl or alkenyl group having 1 to 37 carbon atoms per group.
Suitable examples of (Ci-C3~) alkyl include, but are not limited to: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, 2-ethylhexyl, octyl, decyl, isodecyl, undecyl, dodecyl (also known as lauryl), tridecyl, tetradecyl (also known as myristyl), pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, cosyl and eicosyl.
Suitable examples of (Ci-C3~) alkenyl include, but are not limited to:
ethenyl, n-propenyl, isopropenyl,1-butenyl, cis-2-butenyl, isobutylene, traps-2-butenyl, 2,3,-dimethyl-2-butenyl, 3-methyl-1-butenyl, 2-methyl-2-butene,1-pentenyl, cis-pentenyl, traps-2-pentenyl,1-hexenyl,1-heptenyl,1-octenyl,1-nonenyl and 1-decenyl.
Suitable examples of (CI-C37) substituted alkyl and alkenyl include, but are not limited to the above recited alkyl and alkenyl groups substituted with:
hydroxy;
halide such as fluorine, chlorine or bromine; cyano; alkoxy; haloalkyl;
carbalkoxy;
carboxy; amino; alkylamino derivatives and the like; and vitro groups.
These tertiary alkyl primary amines rriay be used as a single amine or a mixture of amines, and include but are not limited to: 1,1,3,3-tetramethylbutylamine (PRIMENE TOA); an isomeric mixture of Cib to C~ tertiary alkyl primary amines (PRIMENE JM-T); an isomeric mixture of Cs to Cio tertiary alkyl primary amines (PRIMENE BC-9); an isomeric mixture of Ci2 to Ci4 tertiary alkyl primary amines (PRIMENE 81-R); or mixtures thereof. It is preferred to use PRIMENE BC-9, PRIMFNE 81-R, or mixtures thereof. Most preferred is PRIIIrtENE BC-9.
A chelating agent, or chelant, is a compound which contains two or more electron donor atoms that can form coordinate bonds to a single metal atom. A
chelate compound may be either a neutral molecule or complex ion associated with the appropriate counterion. Chelating agents may be either organic or inorganic, aromatic or aliphatic, linear or cyclic, branched or linear aliphatic. A
broader discussion of chelating agents can be found in an article by W. L. Howard and D. A.
Wilson in Kroschwitz, J. I. (Ed.), Kirk-Othmer Enc~cla, ep dia Of Chemical Teclznotogy, Volume 5, 4~ Edition, J. Wiley: NY (1993), pp. 764-795. For purposes of this invention, those chelants that can form oil soluble complexes with said amines are preferred.
Some of the preferred classes of chelating agents useful in the present invention include: organic acids such as acetic acid, acrylic acid and lauric acid;
arninocarboxylic acids such as ethylenediaminetetraacetic acid, hydroxyethyl-ethylenediaminetriacetic acid, nitrilotriacetic acid, N-dihydroxyethylglycine and ethylenebishydroxyphenyglycine; phosphoric acids such as nitrilotrimethylene-phosphoruc acid, ethylenediaminetetra(methylenephosphonic acid) and hydroxyethylidenediphosphonic acid; polyphosphates such as sodium tripolyphosphate and hexametaphosphoric acid;1,3-diketones such as acetylacetone, trifluoroacetylacetone and thenoyltrifluoroacetone; phenols such as salicylaldehyde, disulfopyrocatechol and chromotropic acid; aminophenols such as oxine, 8-hydroxyquinoline and oxinesulforic acid; oximes such as dimethylglyoxime and salicylaldoxime; sulfur compounds.such as thioglycolic acid and diethyl dithiophosphoric acid; macrocylic compounds such as dibenzo-[18]-crown-6, hexamethyl-[14]-4,11-dieneN4 and (2.2.2-cryptate); polycarboxylic acids such as citric acid and polyp-vinylbenzyliminodiacetic acid); terminally unsaturated acrylic acid oligomers such as described in US 5,710,227 (Freemand et al:); other polymeric compounds such as polymethacryloylacetone; and salts of such compounds, as appropriate. It is most preferred to use ~iOAc, EDTA, NTA and their salts.
Most preferred are EDTA and its salts.
The following examples are presented to illustrate further various aspects of the present invention, but are not intended to limit the scope of the invention in any respect.
Examples 1-11 illustrate the prepaxation of various complexes of the present invention.
Example 1 To a 3-necked round bottom flask equipped with a rnecharucal stirrer, heating mantle, addition funnel and reflux condenser was added 0.5 moles of an isomeric mixture of Ciz to Ci4 tertiary alkyl primary amines. The mixture was heated to about 60 °C, at which time 0.2 moles of EDTA was slowly added to the amine mixture through the additional funnel, with stirring, to maintain the temperature between 80 and 100 °C. When addition was completed, the reaction temperature was raised to 120-140 °C and maintained for about an hour (or until the EDTA was completely dissolved). The pH of the mixture was checked, and if below 8.5, additional amine was added. The reaction mixture was then allowed to cool to room temperature.
Example 2 To a 3-necked round bottom flask equipped with a mechanical stirrer, heating mantle, addition funnel and reflux condenser was added 0.26 moles of an isomeric mixture of Ci2 to Cia tertiary alkyl primary amines and 113 g of toluene. The mixture was heated to about 60 °C, at which time 0.057 moles of EDTA
was slowly added to the amine and toluene mixture through the additional funnel, with stirring, to maintain the temperature between 80 and 100 °C. When addition was completed, the reaction temperature was maintained at 100 °C for about four hours (or until the EDTA was completely dissolved). The pH of the mixture was checked, and if below 8.5, additional amine was added. The reaction mixture was then allowed to cool to room temperature. .
Example 3 To a 3-necked round bottom flask equipped with a mechanical stirrer, heating mantle, addition funnel and reflux condenser was added 0.9 moles of an isomeric mixture of Cs to Cio tertiary alkyl primary amines. The mixture was heated to about 60 °C, at which time 0.05 moles of EDTA was slowly added to the amine and toluene mixture through the additional funnel, with stirring, to maintain the temperature between 80 and 100 °C. When addition was completed, the reaction temperature 15~ was maintained at 100 °C for about four hours. The pH of the mixture was checked, and if below 8:5, additional amine was added. The reaction mixture was then allowed to cool to room temperature.
Example 4 To a 3-necked round bottom flask equipped with a mechanical stirrer, heating mantle; addition funnel and reflux condenser was added 0.26 moles of an isomeric mixture of Cs to Cio tertiary alkyl primary amines and 103 g of kerosene. The mixture was heated to about 60 °C, at which time 0.02 moles of NTA was slowly added to the amine and toluene mixture through the additional funnel, with stirnng, to maintain the temperature between 80 and 100 °C. When addition was completed, the reaction temperature was maintained at 100 °C for about four hours.
The pH of the mixture was checked, and if below 8.5, additional amine was added. The reaction mixture was then allowed to cool to room temperature.
Example 5 To a 3-necked round bottom flask equipped with a mechanical stirrer, heating mantle, addition funnel and reflux condenser was added 0.3 moles of an isomeric mixture of Clo to C14 tertiary alkyl primary amines and 103 g of kerosene. The mixture was heated to about 60 °C, at which time 0.02 moles of NTA was slowly added to the amine and toluene mixture through the additional funnel, with stirring, to maintain the temperature between 80 and 100 °C. ~Nhen addition was completed, the reaction temperature was maintained at 100 °C for about four hours.
The pH of the mixture was checked, and if below 8.5, additional amine was added. The reaction mixture was then allowed to cool to room temperature.
Example 6 To a 3-necked round bottom flask equipped with a mechanical stirrer, heating mantle; addition funnel and reflux condenser was added 85.9 g of Example 3 and 38.8 g of Cs to Cio tertiary alkyl prunary amines. The mixture was heated to about 100 °C for an hour or until the mixture was clear. The reaction mixture was then allowed to cool to room temperature.
Example 7 To a 3-necked round bottom flask equipped with a mechanical stirrer, heating mantle, addition funnel and reflux condenser was added 40 g of the mixture from Example 6 and 40 g of toluene. The mixture was mixed until homogeneous and clear.
Example 8 To the material from Example 4, 59 g of isopropanol was added and mixed until the material was clear.
Example 9 To a 3-necked round bottom flask equipped with a mechanical stirrer, heating mantle, addition funnel and reflux condenser was added 0.34 moles of an isomeric mixture of Cib to C~ tertiary alkyl primary amines. The mixture was heated to about 60 °C, at which time 0.12 moles of acetic acid was slowly added to the amine mixture through the additional funnel, with stirring, to maintain the temperature between 80 and 100 °C. When addition was completed, the reaction temperature was raised to 120-140 °C and maintained for about an hour (or until the mixture was completely clear). The pH of the mixture was checked, and if below 8.5, additional arriine was added. The reaction mixture was then allowed to cool to room temperature.
Example 10 To a 3-necked round bottom flask equipped with a mechanical stirrer, Beating mantle, addition funnel and reflux condenser was added 0.33 moles of an isomeric mixture of Cib to Czz tertiary allcyl primary amines. The mixture was heated to about 60 °C, at which time 0.05 moles of citric acid was slowly added to the amine mixture through the additional funnel, with stirring, to maintain the temperature between 80 and 100 °C. When addition was completed, the reaction temperature was raised to 120-140 °C and maintained for about an hour (or until the citric acid was completely dissolved). The pH of the mixture was checked, and if below 8.5, additional amine was added. The reaction mixture was then allowed to cool to room temperature.
Facam~le 11 To a 3-necked round bottom flask equipped with a mechanical stirrer, heating mantle, addition funnel and reflux condenser is added 0.9 moles of AMBERLITE
LA-2. The mixture was heated to about 60 °C, at which time 0.1 moles of nitrilotrimethylene-phosphoric acid is slowly added to the amine mixture through the additional funnel, with stirnng, to maintain the temperature between 80 and 100 °C. When addition is completed, the reaction temperature is raised to 120 -140 °C
and maintained for about an hour (or until the mixture is clear). The pH of the mixture is checked, and if below 8.5, additional AMBERLITE LA-2 is added. The reaction mixture is then allowed to cool to room temperature.
In the following Examples 12-16, the viscosity measurements were made using a Brookfield viscometer Model DV-III equipped with a THERMOSEL system - i4 -i (Brookfield Engineering Laboratories, Inc., Stoughton, MA) and a temperature controller with an RTD (remote temperature detector) probe. The THERMOSEL
system consists of a heating chamber, a removable sample chamber, an SC4.spindle and an insulating cap. As the THERMOSEL system requires only 8 mL of sample, the sample temperature is readily controlled and the viscosity is more accurately measurable Example 12 This Example illustrates the effect of complex concentration on the viscosity of Venezuelan Heavy Crude Oil. In this Example, the additive was the complex of Example 1.
Sample Additive Temp = 75 F (24 C) Temg. =150 F (66 C) ID (ppm) Viscosity cps)% ReductionViscosity % Reduction (cps) 750 3000 25.0 250 19.9 1000 2950 26.2 242 22.4 1250 2850 28.8 235 24.7 1750 2650 33.8 212 32.0' _ _2_000 ___2350__ _4_1.2 ___ 207 __3_3.6 _ _ 0 56000 - 2050 _ 750 38000 32.1 1700 17.1 1000 32000 42.8 1600 22.0 1250 27500 50.1 1500 26.8 1750 24500 56.2 1350 34.1 2000 23500 _ 58.0 1250 _ 39.0 -- - -- --- ---. 1-C 0 __ 7900 --750 --- --- 6200 21.5 1000 - - 6150 22.2 1250 - - 6000 24.0 1750 ~ - - 4600 41.8 _ _2_000 ___ -_ ___-- __ 3800_ __5_1.9 -__ _ 750 83000 2.4 2900 23.7 1000 70500. 17.0 2500 34.2 1250 58000 31.8 2400' 36.8 1750 51000 40.0 2300 39.5 2000 42500 50.0 1750 53.9 I
Example 13 This Example further illustrates the effect of complex concentration on the viscosity of Venezuelan Heavy Crude Oil. In this Example, the additive was the complex of Example 1.
Sample Additive Tem~,=110 F X43 C~ Temp =120 F (49 C~
ID . (ppm) Viscosity % ReductionViscosity % Reduction (cps) (cps) 500 38000 20.0 20000 25.9 1000 30000 36.8 16500 38.9 1500 22000 53:7 11500 57.4 ___ _2_000 _ _17500 ___63.2 ___8000 _ 70.4__ 1-F 0 _ - _ 500 9004 15.1 5800 10.8 1000 7500 29.2 5100 21.5 1500 6900 35.0 4800 26.2 2000 5900_ 44.3 4200_ 35.4 -- --- -- --- --~--_ 500 950 2.6 675 10.6 1000 725 25.6 550 27.2 1500 625 35.9 460 39.1 ___ _2_000 ___ 600_ ___38.5 _ 425_ __4_3.7__ -500 3000 11.8 ~ 2350 14.5 1000 2550 25.0 1950 29.1 1500 2200 35.3 1600 41.8 2000 1950 42.6 1400 49.1 Example 14 This Example illustrates the effect of complex concentration on the viscosity of pipeline HCO at various temperatures. In this Example, the adclitive was the complex of Example 1.
Temp. (°F/°C) Additive (ppm) Viscosity (cps) % Reduction 75/ 24 0 ' 6580 --750 5650 17.5 1000 5450 20.4 1250 5200 ~ 24.1 1750 4500 34.3 I
._ - 90/32 -- - - 0 - - - ~~_. - - - _ 750 2312 19.3 1000 2125 25.8 1250 1875 34.6 ____ __ 175_0 __ 14_62_ _ 4_9.0 ~ - !
__ 492 -750 440 10.6 1000 420 ~ 14.6 1250 390 20.7 1750 340 30.9 Examyle 15 This Example further illustrates the effect of complex concentration on the viscosity of flow station HCO at various temperatures. In the Table below, the Sample ID numbers correspond to Example numbers. For example, 9 means that the additive was the complex of Example 9.
Sample Additive Temp = 75 F 24 C) Temp =15U
~ F f66 C1 ID (ppm) Viscosity (cps)% ReductionViscosity % Reduction (cps) C_ont_rol_ _ 0 _ _ 1280_0 _- _ _ _ 825_ _ _ _- _ ~ _ --_ 750 10000 21.9 680 17.6 1000 10600 17.2 665 19.4 1250 9000 29.7 640 22.4 _1500 _ _ _ 880_0 _ _31.2 _ _ 630_ _ _23.6 _ _ -_ _ ! 750 8300 35.2 ~ 710 13.9 1000 8400 34.4 670 18.8 1250 9600 25.0 550 33.3 1500 ___ 640_0 __50.0 __ 560_ __32.1 _ i ___ __ 10800 15.6 _ _ 17 750 800 3.0 1000 10600 17.2 650 21.2 1250 9000 29.7 655 _ . 20.6 1500 10000 21.9 540 - 34.5 Example 16 This example further demonstrates that the viscosity reduction obtained by addition of the complexes of the present invention to samples of Venezuelan HCO is not affected by different diluents.
Additive A-3 was made by diluting the complex of Example 3 with toluene, and Additive B-4 was made by diluting the complex of Example 4 with kerosene.
Both complexes were diluted to 10% active.
Additive Temperature Viscosity (cps)% Reduction (C) None 21 118655 ____ 40 3_1253 --- - - - - , - - - - - -2000 ppm (A-3)21 82182 30.7 _ _ _ _ _ 40 8432 73.0 _ _ - - -- . -r - - - - -- -2000 ppm (B-4)21 73304 38.2 - ~
40 7507 76.0
Claims (7)
1. A method for reducing viscosity of heavy crude oils in significantly non-reversible manner, comprising the steps of: adding a viscosity-reducing amount of an amine-chelate complex formed by heating together at least one organic amine and at least one chelating agent to a heavy crude oil, and dispersing the amine-chelate complex throughout a portion of the heavy crude oil.
2. The method of claim 1, wherein the chelating agent is selected from the group consisting of: carboxylic acids, aminocarboxylic acids; phosphoric acids;
polyphosphates; 1,3diketones; phenols; aminophenols; oximes; sulfur compounds;
macrocyclic compounds; polycarboxylic acids; terminally unsaturated acrylic acid oligomers; and salts thereof.
polyphosphates; 1,3diketones; phenols; aminophenols; oximes; sulfur compounds;
macrocyclic compounds; polycarboxylic acids; terminally unsaturated acrylic acid oligomers; and salts thereof.
3. The method of claim 1, wherein the chelating agent is selected from the group consisting of: acetic acid, ethylene diaminetetraacetic acid, nitrilotriacetic acid and salts thereof.
4. The method of claim 1, wherein the organic amine is selected from the group consisting of: aliphatic (C1-C40) primary monoamines; polyalkylamines;
tertiary monoamines; saturated or substantially saturated aliphatic (C1-C40) secondary amines; and polyamines selected from straight or branched-chain alkanes containing two or more amino groups, at least one of which is a primary amino group.
tertiary monoamines; saturated or substantially saturated aliphatic (C1-C40) secondary amines; and polyamines selected from straight or branched-chain alkanes containing two or more amino groups, at least one of which is a primary amino group.
5. The method of claim 4, wherein the organic amine comprises an amine selected from the group consisting of: 2-ethylhexylamine, C4-C40 tertiary alkyl primary amines, tridecylamine, polyisobutylamine, oleylamine, di(cyclohexyl)amine, C4-C49 long chain alkyl amines and trioctylamine.
6. The method of claim 5, wherein the amine comprises a tertiary alkyl primary amine of formula:
wherein R1, R2, and R3 are each independently selected from: (C1-C37) alkyl;
substituted (C1-C37) alkyl; (C1-C37) alkenyl or substituted (C1-C37) alkenyl.
wherein R1, R2, and R3 are each independently selected from: (C1-C37) alkyl;
substituted (C1-C37) alkyl; (C1-C37) alkenyl or substituted (C1-C37) alkenyl.
7. The method of claim 6, wherein 0.01 to 50 weight percent of the amine-chelate complex is mixed with an organic solvent.
The method of claim 7, wherein the weight percent of the amine-chelate complex is 0.01 to 10.
The method of claim 7, wherein the weight percent of the amine-chelate complex is 0.01 to 10.
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US12249699P | 1999-03-02 | 1999-03-02 | |
US60/122,496 | 1999-03-02 |
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CA2299104C true CA2299104C (en) | 2004-05-04 |
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EP (1) | EP1033471B1 (en) |
CN (1) | CN1205404C (en) |
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CO (1) | CO5210976A1 (en) |
MX (1) | MXPA00001955A (en) |
NO (1) | NO326829B1 (en) |
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US20040232042A1 (en) * | 2003-05-23 | 2004-11-25 | Ravindranath Mukkamala | Amine-acid reaction products as asphaltene dispersants in crude oil |
US20040232044A1 (en) * | 2003-05-23 | 2004-11-25 | Ravindranath Mukkamala | Oil-soluble imine-acid reaction products as asphaltene dispersants in crude oil |
US7097759B2 (en) * | 2003-05-23 | 2006-08-29 | Rohm And Haas Company | Carbonyl, thiocarbonyl or imine containing compounds as asphaltene dispersants in crude oil |
US7122112B2 (en) * | 2003-05-29 | 2006-10-17 | Rohm And Haas Company | Compounds containing amide and carboxyl groups as asphaltene dispersants in crude oil |
US7435333B2 (en) * | 2004-07-02 | 2008-10-14 | Exxonmobil Research And Engineering Company | Upgrading asphaltene containing oils |
US7674365B2 (en) | 2004-10-07 | 2010-03-09 | Rohm And Haas Company | Formulations useful as asphaltene dispersants in petroleum products |
CA2568764A1 (en) * | 2005-12-07 | 2007-06-07 | Rohm And Haas Company | Asphaltene dispersants for petroleum products |
US8062512B2 (en) * | 2006-10-06 | 2011-11-22 | Vary Petrochem, Llc | Processes for bitumen separation |
US7758746B2 (en) | 2006-10-06 | 2010-07-20 | Vary Petrochem, Llc | Separating compositions and methods of use |
CN101589135B (en) | 2006-10-06 | 2014-04-02 | 瓦里石化有限责任公司 | Separating compositions and methods of use |
US8394872B2 (en) | 2009-07-10 | 2013-03-12 | Nalco Company | Method of reducing the viscosity of hydrocarbon fluids |
AU2010292142B2 (en) | 2009-09-10 | 2014-11-06 | Board Of Regents, The University Of Texas System | Process of using hard brine at high alkalinity for enhanced oil recovery (EOR) applications |
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AR081549A1 (en) * | 2010-05-25 | 2012-10-03 | Univ Texas | FORMULATIONS OF ALKALINE POLYMERS WITHOUT SURFACTANT TO RECOVER REACTIVE CRUDE OIL |
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US20140323369A1 (en) * | 2013-04-24 | 2014-10-30 | Upali P. Weerasooriya | Use of amines in heavy oil transport |
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US11566164B2 (en) | 2017-07-06 | 2023-01-31 | Innospec Oil Field Chemicals Llc | Compositions and methods and uses relating thereto |
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- 2000-02-22 CA CA002299104A patent/CA2299104C/en not_active Expired - Lifetime
- 2000-02-23 CO CO00012704A patent/CO5210976A1/en active IP Right Grant
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- 2000-02-24 MX MXPA00001955A patent/MXPA00001955A/en active IP Right Grant
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- 2000-03-02 CN CN00103678.5A patent/CN1205404C/en not_active Expired - Lifetime
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US6402934B1 (en) | 2002-06-11 |
EP1033471B1 (en) | 2003-09-17 |
NO20000903D0 (en) | 2000-02-24 |
CO5210976A1 (en) | 2002-10-30 |
CN1265446A (en) | 2000-09-06 |
EP1033471A1 (en) | 2000-09-06 |
CA2299104A1 (en) | 2000-09-02 |
MXPA00001955A (en) | 2002-03-08 |
CN1205404C (en) | 2005-06-08 |
NO20000903L (en) | 2000-09-04 |
NO326829B1 (en) | 2009-02-23 |
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